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note
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Upon exposure of a diastereomixture of 44b and 45b (44b : 45b=10:90) to the cyclization conditions at 70 ° C for 4 h, an isomerized mixture was obtained in 53% yield (44b : 45b=60 : 40). However, this palladium-catalyzed isomerization cannot explain the observed cis selectivity in DMF (44 : 45=100 : 1).
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As shown in Chart 10, the cis cyclization to give 121 (Chart 14) would be the predominant process over the trans cyclization.
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150
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26444497560
-
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see: ref. 20
-
The starting amino alcohols 129 and 132 were readily prepared from natural amino acids through alkynylation of the corresponding aldehydes, see: ref. 20.
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151
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0038076018
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0035793267
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167
-
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26444569281
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note
-
The trans-configuration of 169 was determined by NOE analysis as shown below. Chemical Presented
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-
-
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168
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0002538829
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0032481580
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0032481404
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180
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16244407181
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For authors' recent contribution on the allene chemistry, see: Hamaguchi H., Kosaka S., Ohno H., Tanaka T., Angew. Chem., Int. Ed., 44, 1513-1517 (2005).
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23944509694
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For authors' recent contribution on the allene chemistry, see: Ohno H., Mizutani T., Kadoh Y., Miyamura K., Tanaka T., Angew. Chem., Int. Ed., 44, 5113-5115 (2005).
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23944434406
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For authors' recent contribution on the related enyne chemistry, see: Ohno H., Yamamoto M., Iuchi M., Tanaka T., Angew. Chem., Int. Ed., 44, 5103-5106 (2005).
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